Measurement uncertainty of shikimic acid in red wines produced in Chile

High-performance liquid chromatography (HPLC) to determine shikimic acid is used as a complementary tool to differentiate wine varieties. In order to correctly classify, measurement uncertainty of shikimic acid by HPLC in red wine was estimated considering the following components: uncertainty associated with the preparation of shikimic acid stock solution, uncertainty associated with quantification using a calibration curve, and uncertainty associated with precision. The most important contribution to total uncertainty was the method precision. The expanded uncertainty (U) for different wine varieties was between 2.6 and 8.5%. The method was applied to determine the concentration of shikimic acid in different emerging wine varieties cultivated in Chile, such as Carmenère, Shiraz, and Pinot Noir, comparing them with classical varieties, such as Cabernet Sauvignon and Merlot. Shiraz wines presented lower shikimic acid concentrations (between 27 and 86 mg L⁻¹ with U _(k=2) = 2.6%) than Cabernet Sauvignon wines (between 41 and 142 mg L⁻¹ with U _(k=2) = 8.1%), but their concentrations were higher than found in Merlot (from 9 to 41 mg L⁻¹ with U _(k=2) = 4.3%) and Carmenère wines (between 7 and 49 mg L⁻¹ with U _(k=2) = 5.8%). Pinot Noir was the variety with the lowest concentration of this acid (7–14 mg L⁻¹ with U _(k=2) = 8.5%). Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

毛细管区带电泳-间接紫外法快速测定食品中的甜蜜素

建立了毛细管区带电泳-间接紫外法快速测定食品中甜蜜素的新方法。液体样品用超纯水稀释后直接进样;固体样品经粉碎或剪碎后用超纯水超声提取后离心,上清液直接进样或用水稀释后进样。以未涂敷石英毛细管（80 cm×75 μm,有效长度：70 cm）为分离柱,以2 mmol/L苯甲酸钠+10 mmol/L碳酸钠+0.5 mmol/L十六烷基三甲基溴化铵为分离缓冲液;于200 nm波长处检测。检出限为8.9 mg/kg （S/N=3）,定量限为26.7 mg/kg （S/N=9）。低、中、高添加水平的加标回收率分别为93.4%、100.3%及101.9%,相应的RSD分别为6.7%、2.0%及2.2%（n=5）。日内及日间精密度分别为2.6%和4.5%。整个分析过程无需有机溶剂。在能力验证样品的分析结果与国家标准方法的结果相吻合的基础上,分析了7件食品样品,获满意结果。     

毛细管区带电泳-间接紫外检测法快速测定食品中乳糖、蔗糖、葡萄糖和果糖

建立了毛细管区带电泳-间接紫外检测快速测定食品中乳糖、蔗糖、葡萄糖和果糖的方法。以水或5 mmol/L醋酸为样品提取液,未涂层熔融石英毛细管(30.2 cm(有效长度20 cm)×50 μm)为分离柱,4 mmol/L山梨酸钾+10 mmol/L磷酸钠+30 mmol/L NaOH(pH 12.56)+0.5 mmol/L十六烷基三甲基溴化铵(CTAB)为分离缓冲液,在-8 kV下分离,于254 nm波长下检测,10 min内实现了食品中上述4种糖的同时分离与测定。乳糖、蔗糖、葡萄糖和果糖的检出限(S/N=3)分别为50、75、25和25 mg/L,定量限(S/N=10)分别为150、225、75和75 mg/L,回收率在87.0%~107.0%之间,相对标准偏差在1.2%~4.7%之间。整个实验过程未使用有机溶剂。用该法测定了9种食品样品及1个质控样品,结果表明该法简单、快速、准确,适用于食品中乳糖、蔗糖、葡萄糖和果糖的日常测定。     

非衍生化毛细管区带电泳直接紫外检测法测定茶叶中的4种氨基酸

采用非衍生化毛细管区带电泳直接紫外检测法同时分离测定精氨酸(Arg)、色氨酸(Trp)、苯丙氨酸(Phe)和酪氨酸(Tyr)4种氨基酸,并应用于不同发酵过程的茶叶样品的测定。在分离电压为20 kV、柱温为25 ℃、检测波长为190 nm条件下,以25 mmol/L硼酸-硼砂缓冲溶液(pH 10.0)为运行缓冲液,4种组分在8 min内达到基线分离,Arg、Trp、Phe、Tyr的检出限分别为5.0,1.0,0.3和0.5 mg/L。7次平行测定中,4种组分迁移时间的相对标准偏差(RSD)均小于2.8%,峰电流的RSD均小于4.0%。将所建立的方法用于11种实际茶叶样品中Arg、Trp、Phe和Tyr含量的测定,结果令人满意。该方法可以为茶叶的质量评估提供借鉴。     

Separation of metal cations in acidic solution by capillary electrophoresis with direct and indirect UV detection

Methods for the detectionn of metal cations under acidic conditions, near PH 2, in capillary electrophoresis (CE) were investigatged. Conditions for direct UV detection of UV absorbing metal cations such as Cr³⁺, Cu²⁺, Fe³⁺, UO₂²⁺, VO²⁺, and VO²⁺ were established With aqueous HCl or HClO₄ as the electroyte carrier. The speciation of vanadium(IV) and vanadium(V) at PH 2.3 by CE was achieved with direct detection at 185 nm. With the strong absorbance at 185 nm, no complexation was needed to detect the metal cations. An indirect UV detrection scheme for acidic conditions was also investigated. Several background carrier electolytes (BCES) were studied including 4-methylbenzylamince, nicontinamide, pyridazine, guanidine, 3-picoline, and chromium (III) to determine their effectivencess under very acidic conditions. The efect of ioni c surfactants and the nonionic surfactant, Trition X-100, on the peak heights and N Values was also studied.     

高效液相色谱-间接光度检测法测定己内酰胺酸团中的正己烷含量

采用在流动相中添加有紫外吸收的本底试剂的方法,利用高效液相色谱-间接光度检测法直接测定己内酰胺酸团中无紫外吸收的正己烷含量。考察了流动相组成、本底试剂的种类和浓度、波长梯度等对测定的影响。确定的高效液相色谱条件: 色谱柱为Agilent HC-C18柱(250 mm×4.6 mm, 5 μm),流动相为含1.17 mmol/L 1,5-萘二磺酸(本底试剂)的甲醇-水(85:15, v/v)溶液,柱温为35 ℃,流速为1.0 mL/min,并采用设定波长梯度的方法调整系统峰和被测峰的相对大小。该分析方法的线性范围为0.5～20 mg/kg,相关系数为0.99993,相对标准偏差为2.53%,检出限为0.03 mg/kg,加标回收率为98.45%～102.3%。方法简单,选择性好,灵敏度高,抗干扰强,可快速准确地测定实际样品中的正己烷。     

High-performance liquid chromatography determination of nitrated polycyclic aromatic hydrocarbons by indirect fluorescence detection

A high-performance liquid chromatography (HPLC) method for the analysis of nitrated polcyclic aromatic hydrocarbons (NPAHs) is reported. NPAH mixtures were pre-concentrated using solid-phase extraction and well resolved on a C(18) column. They were detected using an indirect method involving the quenching of the emission from the fluorophores 5,6,7,8-tetrahydronaphthol (5,6,7,8-THN-1-OH), 7-amino-4-methyl coumarin (Coumarin 120, COU-120) and 3-hydroxy-4-(2-hydroxy-4-sulfo-1-naphthylazo)2-naphthalene carboxylic acid (Calcon carboxylic acid, CCA). Linear calibration curves were obtained in the range 1.1 x 10(-9) to 1.1 x 10(-8) mol/L. Using COU 120 as the fluorophore, the detection limit was 2.9 x 10(-10) mol/L for 1-nitronaphthalene and 2.1 x 10(-11) mol/L for 2-nitrofluorene. Recoveries of NPAHs from spiked tap water samples were between 88 and 100%.     

Separation and determination of pyrrolidinium ionic liquid cations by ion chromatography with direct conductivity detection

A method for rapid and simultaneous determination of multiple pyrrolidinium ionic liquid cations by ion chromatography with direct conductivity detection was developed.Chromatographic separations were performed on a cation exchange column using ethylenediamine-acetonitrile as the mobile phase.The effects of chromatographic column and the mobile phase,as well as the column temperature on the retention of the cations were investigated.The retention rules of the cations under different chromatographic conditions were formulated.The retention of the cations followed the carbon number rule.The method has been successfully applied to the determination of three ionic liquids synthesized by a chemical laboratory.     

Optimization and validation of a method for the direct determination of catechin and epicatechin in red wines by HPLC/fluorescence

The present paper describes a direct procedure for the determination of catechin and epicatechin concentrations in red wines employing reverse-phase high performance liquid chromatography (RP HPLC) and detection by fluorescence. The method was performed using a sample volume of 10 µL without dilution. The separation process employed a Chromolith performance RP-18e (100 mm × 4.6 mm) column, and the mobile phase was composed of solvent A: methanol-acetic acid-water (90:8:2) and solvent B: water-acetic acid-methanol (10:2:88) at a flow rate of 1.0 mL min^− 1. Linearity was observed in the range of 1 to 30 mg L^− 1, with limits of detection and quantification of 0.27 and 0.89 mg L^− 1, respectively, for catechin and 0.33 and 1.01 mg L^− 1, respectively, for epicatechin. The precisions estimated by the relative standard deviation were 3.34 and 1.09% for catechin concentrations of 0.5 and 20 mg L^− 1 respectively and 2.82 and 0.49% for epicatechin concentrations of 0.5 and 20 mg L^− 1, respectively. The evaluation of the accuracy was done using an addition/recovery assay. Four wine samples were used, and the recoveries varied from 105 to 108% for catechin and from 97 to 119% for epicatechin. The method was applied to the analysis of red wine samples collected from the São Francisco region, Bahia State, Brazil. Nine samples were analyzed, and the catechin and epicatechin concentrations varied from 7.51 to 73.20 and from 5.08 to 43.32 mg L^− 1, respectively. The concentrations found agree with data reported in the literature.     

Simultaneous determination of catecholamines by ion chromatography with direct conductivity detection

A simple method for simultaneous determination of three catecholamines using ion chromatography (IC) with direct conductivity detection (CD) based on the ionization of catecholamines in acidic medium without chemical suppression is developed in the present paper. The method could be used for the determination of these catecholamines in pharmaceutical preparations for the purpose of drug quality control. The recovery of catecholamines was more than 97% (n=3) and the relative standard deviation (R.S.D.) (n=11) was less than 2.1%. In a single chromatographic run, norepinephrine (NE), epinephrine (E) and dopamine (DA) can be determined in less than 10 min. The detection limits were found to be 0.001 μg/ml for NE, 0.01 μg/ml for E and DA respectively. Linear ranges were 0.01–50 μg/ml for NE (r²=0.9998), 0.1–50 μg/ml for E (r²=0.9995) and DA (r²=0.9999), respectively.     

离子色谱法-间接紫外检测离子液体中三种含氟酸根阴离子

建立了离子色谱-间接紫外检测法同时分析离子液体中的三氟乙酸根(CF3COO-)、四氟硼酸根(BF4-)和三氟甲烷磺酸根(CF3SO3-)的方法。用Shodex IC NI-424阴离子交换柱作为分离柱,探讨了影响上述三种离子保留和检测的因素及其保留规律。最终选用色谱条件为:以1.75 mmol·L-1邻苯二甲酸-1.68 mmol·L-1三(羟甲基)氨基甲烷为淋洗液,柱温45℃,流速1.0 m L·min-1,UV检测波长设定在265 nm。在此条件下,可实现上述三种阴离子的同时分析,且色谱峰形良好。所测阴离子的检出限(S/N=3)为0.39~1.57 mg·L-1,保留时间和峰面积的相对标准偏差(n=5)均在1%以下。将此方法应用于测定离子液体中的三氟乙酸根、四氟硼酸根及三氟甲烷磺酸根,加标回收率为99%~102%。该方法简单、准确、可靠,具有较好的实用性。     

Separation and determination of homovanillic acid and vanillylmandelic acid by capillary electrophoresis with electrochemical detection

A method of separation and determination of homovanillic acid (HVA) and vanillylmandelic acid (VMA) was developed based on capillary zone electrophoresis/amperometric detection with high sensitivity, good resolution and selectivity. In order to achieve complete separation and good response, several factors including pH, buffer concentration, separation voltage, detection potential and the length of separation capillary, were studied in detail. The method has been used to determine both HVA and VMA in human urine. Uric acid (UA) in human urine did not interference with their determination. The limit of detection of the method was 1.3×10⁻⁶ mol/l (1.4 fmol) for HVA and 7.9×10⁻⁷ mol/l (0.87 fmol) for VMA at a signal-to-noise ratio of 3.     

Potential of microcolumn liquid chromatography and capillary electrophoresis with flame photometric detection for determination of polar phosphorus-containing pesticides

Summary The potential of microcolumn liquid chromatography (μlC) and capillary electrophoresis (CE) with on-line, flame photometric detection (FPD) in the P-selective mode has been studied for determination of polar P-containing pesticides, glyphosate and its main metabolite, aminomethylphosphonic acid (AMPA), ethephon, fosetyl-aluminium and acephate. Acephate was determined by reversed-phase μLLC-FPD using large-volume injections with peak compression, the other compounds were determined by μLC-FPD and CE-FPD using simple, large-volume injection procedures to obtain limits of detection of 7.5-500 ng·mL⁻¹ and 1.0 μ·mL⁻¹, respectively. The methods showed acceptable repeatability and robustness and were successfully applied for rapid and selective determination of pesticides in fruit, vegetable and water samples.     

New preconditioning strategy for the determination of inorganic anions with capillary zone electrophoresis using indirect UV detection

It is widely accepted that preconditioning procedures are indispensable in capillary electrophoresis in order to achieve reproducibility of migration times and peak areas. Several preconditioning strategies have been employed for electrophoretic determinations of inorganic anions using indirect UV detection including simple flushing with buffer or alkaline or acid pre-rinsing followed by flushing with electrolyte. We investigated the influence of various preconditioning strategies on the reproducibility of migration times and peak areas of inorganic anions. The electrolyte systems for indirect UV detection were based on pyromellitic acid and chromic acid respectively as UV absorbing probes and hexamethonium hydroxide as electroosmatic flow modifier. Preconditioning agents under investigation were electrolyte buffer, NaOH, HCl and the free acids of the UV absorbing probes. Investigations showed that reproducibility of migration times and peak areas can be significantly improved by acid pre-rinsing using the corresponding acid of the UV absorbing probes compared to preconditioning by flushing the capillary with buffer. In contrast to acid pre-rinsing using hydrochloric acid no interfering signals within the migration time window of inorganic anions under investigation can be observed. The optimized preconditioning procedure yields relative standard deviations of migration times less than 0.25% (n=10). Relative standard deviations of corrected peak areas were below 5% applying acid preconditioning using pyromellitic acid.     

Metal ion capillary zone electrophoresis with direct UV detection: Comparison of different migration modes for negatively charged chelates

Summary Several migration modes suitable for capillary zone electrophoretic (CZE) separation of metal ions in the form of 8-hydroxyquinoline-5-sulphonic acid complexes are described and compared. Superior analysis time, resolution, efficiency and detectability were achieved using reversed movement of anionic metal complexes (in the anode-to-cathode direction) under the action of the electroosmotic flow. This method allows the CZE analysis of multicomponent mixtures of transition metal ions as well as aluminium within about six minutes.     

Comparison between micellar liquid chromatography and capillary zone electrophoresis for the determination of hydrophobic basic drugs in pharmaceutical preparations

The determination of highly hydrophobic basic compounds by means of conventional reversed-phase liquid chromatographic methods has several drawbacks. Owing to the characteristics of micellar liquid chromatography (MLC) and capillary electrophoresis (CE), these techniques could be advantageous alternatives to reversed-phase chromatographic methods for the determination of these kinds of compounds. The objective of this study was to develop and compare MLC and CE methods for the determination of antipsychotic basic drugs (amitryptiline, haloperidol, perphenazine and thioridazine) in pharmaceutical preparations. The chromatographic determination of the analytes was performed on a Kromasil C(18) analytical column; the mobile phase was 0.04 m cetyltrimethylammonium bromide (CTAB), at pH 3, containing 5% 1-butanol, at a flow rate of 1 mL/min. The CE separation was performed in a fused-silica capillary with a 50 mm tris-(hydroxymethyl)-aminomethane buffer, pH 7, at an applied voltage of 20 kV, using barbital as internal stardard. The proposed methods are suitable for a reliable quantitation of these compounds in the commercial tablets and drops in terms of accuracy and precision and require a very simple pre-treatment of the samples. By comparing the performance characteristics and experimental details of the MLC and CE methods we conclude that CE seems to be slightly better than MLC in the determination of highly hydrophobic compounds in pharmaceuticals in terms of resolution and economy, taking into account that the limits of detection are not a handicap in pharmaceutical samples.     

Simultaneous determination of aminothiols, ascorbic acid and uric acid in biological samples by capillary electrophoresis with electrochemical detection

A method based on capillary electrophoresis with electrochemical detection has been employed for the separation and determination of homocysteine, cysteine, reduced glutathione, ascorbic acid and uric acid. Effects of several important factors such as the acidity and concentration of the running buffer, separation voltage, injection time and detection potential were investigated to acquire the optimum conditions. The detection electrode was a 500 microm diameter platinum disk electrode at a working potential of +1.05 V (vs saturated calomel electrode). The five analytes were well separated within 10 min in a 50 cm long fused silica capillary at a separation voltage of 18 kV in a 100 mm phosphate buffer (pH 7.8). The relation between peak current and analyte concentration was linear over about 3 orders of magnitude with the detection limits (S/N = 3) ranging from 0.83 to 2.58 microm. The proposed method was successfully applied to determine cysteine, reduced glutathione, ascorbic acid and uric acid in human whole blood and rat brain tissues with satisfactory assay results and should find a wide range of bioanalytical applications.     

Selective determination of famotidine in human plasma by high performance liquid chromatography in alkaline media with solid phase extraction

A new method is described for the determination of famotidine by solid phase extraction from alkalinized human plasma followed by reversed phase (RP) HPLC in acetonitrile/alkaline buffer with molsidomine as an internal standard. Different acetonitrile/aqueous buffer mobile phases as well as various RP columns were used. Alkaline medium allowed the limit of quantitation to be lowered to 5 ng/mL of plasma as the famotidine gives more intense absorption at about 286 nm (at pH values higher than 7). Moreover, work in alkaline media and at this wavelength is highly selective as peaks corresponding to impurities present in most samples are well separated. A method using a mildly alkaline mobile phase (acetonitrile/10 mM phosphate with 10 mM 1‐heptanesulphonic acid, pH 7.5) was successfully used for determination of famotidine in human plasma in a pharmacokinetic study.